sp‐Carbon‐Conjugated Organic Polymer as Multifunctional Interfacial Layers for Ultra‐Long Dendrite‐Free Lithium Metal Batteries

Abstract Fatal issues in lithium metal anodes (LMA), such as detrimental lithium dendrites growth and fragile solid‐electrolyte interphase (SEI) during the Li plating/stripping process, often hinder the practical application of Li metal batteries (LMBs). Herein, cobalt‐coordinated sp‐carbon‐conjugated organic polymer (Co‐spc‐COP) is constructed as the protective layer for regulating the interface stability of LMA. The unique synergistic beneficial effect of organic functional groups (C≡C linkage, C=N units and aromatic rings) and Co sites not only regulate the Li + coordination environment and rearrange Li + concentration to facilitate its transport by optimizing the electronic density, enhancing the compatibility with electrolyte interface and supplying “external magnetic driving strategy”, but also strengthens the interfacial stiffness with high Young's modulus to better withstand the mechanical stress. These beneficial effects and relative underlying working mode and mechanism of uniform Li plating and rapid Li + migration on the Co‐spc‐COP are also revealed by various in situ / ex situ experimental technologies and theory calculation. The Co‐spc‐COP‐based cell delivers an extraordinary lifespan of 6600 h and ultrahigh capacity retention of 78.3 % (111.9 mAh g −1 ) after 1000 cycles at 1 C. This demonstrated synergistic strategy in Co‐coordinated organic polymer may gain new insights to regulate the uniform and non‐dendritic deposition/dissolution behaviors for highly stable LMBs.